Photolysis (λ > 472 nm) of 2-diazo-3-pentyne (11) affords triplet 1,3-dimethylpropynylidene (MeC3Me, (3)3), which was characterized spectroscopically in cryogenic matrices. The infrared, electronic absorption, and electron paramagnetic resonance spectra of MeC3Me ((3)3) are compared with those of the parent system (HC3H) to ascertain the effect of alkyl substituents on delocalized carbon chains of this type. Quantum chemical calculations (CCSD(T)/ANO1) predict an unsymmetrical equilibrium structure for triplet MeC3Me ((3)3), but they also reveal a very shallow potential energy surface. The experimental IR spectrum of triplet MeC3Me ((3)3) is best interpreted in terms of a quasilinear, axially symmetric structure. EPR spectra yield zero-field splitting parameters that are typical for triplet carbenes with axial symmetry (|D/hc| = 0.63 cm(-1), |E/hc| = ∼ 0 cm(-1)), while theoretical analysis suggests that the methyl substituents confer significant spin polarization to the carbon chain. Upon irradiation into the near-UV electronic absorption (λmax 350 nm), MeC3Me ((3)3) undergoes 1,2-hydrogen migration to yield pent-1-en-3-yne (4), a photochemical reaction that is typical of carbenes bearing a methyl substituent. This facile process apparently precludes photoisomerization to other interesting C5H6 isomers, in contrast to the rich photochemistry of the parent C3H2 system.